Chemistry

Chemistry Syllabus for UPSC Main Examination

Paper-I

1. Atomic Structure: Heisenberg's uncertainty principle, Schrodinger wave equation (time

independent); Interpretation of wave function, particle in one-dimensional box, quantum
numbers, hydrogen atom wave functions; Shapes of s, p and d orbitals.

2. Chemical Bonding: Ionic bond, characteristics of ionic compounds, lattice energy, Born-Haber
cycle; covalent bond and its general characteristics, polarities of bonds in molecules and their
dipole moments; Valence bond theory, concept of resonance and resonance energy; Molecular
orbital theory (LCAO method); bonding in H2+, H2, He2+ to Ne2, NO, CO, HF, and CN-;
Comparison of valence bond and molecular orbital theories, bond order, bond strength and
bond length.

3. Solid State: Crystal systems; Designation of crystal faces, lattice structures and unit cell;
Bragg's law; X-ray diffraction by crystals; Close packing, radius ratio rules, calculation of some
limiting radius ratio values; Structures of NaCl, ZnS, CsCl and CaF2; Stoichiometric and
nonstoichiometric defects, impurity defects, semi-conductors.

4. The Gaseous State and Transport Phenomenon: Equation of state for real gases,
intermolecular interactions and critical phenomena and liquefaction of gases, Maxwell's
distribution of speeds, intermolecular collisions, collisions on the wall and effusion; Thermal
conductivity and viscosity of ideal gases.

5. Liquid State: Kelvin equation; Surface tension and surface energy, wetting and contact angle,
interfacial tension and capillary action.

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6. Thermodynamics: Work, heat and internal energy; first law of thermodynamics. Second law
of thermodynamics; entropy as a state function, entropy changes in various processes, entropy-
reversibility and irreversibility, Free energy functions; Thermodynamic equation of state;
Maxwell relations; Temperature, volume and pressure dependence of U, H, A, G, Cp and Cv α
and β; J-T effect and inversion temperature; criteria for equilibrium, relation between
equilibrium constant and thermodynamic quantities; Nerns theat theorem, introductory idea of
third law of thermodynamics.

7. Phase Equilibria and Solutions: Clausius-Clapeyron equation; phase diagram for a pure
substance; phase equilibria in binary systems, partially miscible liquids-upper and lower critical
solution temperatures; partial molar quantities, their significance and determination; excess
thermodynamic functions and their determination.

8. Electrochemistry: Debye-Huckel theory of strong electrolytes and Debye-Huckel limiting Law

for various equilibrium and transport properties. Galvanic cells, concentration cells;
electrochemical series, measurement of e.m.f. of cells and its applications fuel cells and
batteries. Processes at electrodes; double layer at the interface; rate of charge transfer, current
density; overpotential; electro-analytical techniques: Polarography, amperometry, ion selective
electrodes and their uses.

9. Chemical Kinetics: Differential and integral rate equations for zeroth, first, second and
fractional order reactions; Rate equations involving reverse, parallel, consecutive and chain
reactions; branching chain and explosions; effect of temperature and pressure on rate
constant; Study of fast reactions by stop-flow and relaxation methods; Collisions and transition
state theories.

10. Photochemistry: Absorption of light; decay of excited state by different routes;

photochemical reactions between hydrogen and halogens and their quantum yields.

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11. Surface Phenomena and Catalysis: Absorption from gases and solutions on solid
adsorbents, Langmuir and B.E.T. adsorption isotherms; determination of surface area,
characteristics and mechanism of reaction on heterogeneous catalysts.

12. Bio-inorganic Chemistry: Metal ions in biological systems and their role in ion transport
across the membranes (molecular mechanism), oxygenuptake proteins, cytochromes and
ferredoxins.

13. Coordination Compounds: (i) Bonding theories of metal complexes; Valence bond theory,
crystal field theory and its modifications; applications of theories in the explanation of
magnetism and electronic spectra of metal complexes. (ii) Isomerism in coordination
compounds; IUPAC nomenclature of coordination compounds; stereochemistry of complexes
with 4 and 6 coordination numbers; chelate effect and polynuclear complexes; trans effect and
its theories; kinetics of substitution reactions in square-planer complexes; thermodynamic and
kinetic stability of complexes. (iii) EAN rule, Synthesis structure and reactivity of metal
carbonyls; carboxylate anions, carbonyl hydrides and metal nitrosyl compounds. (iv) Complexes
with aromatic systems, synthesis, structure and bonding in metal olefin complexes, alkyne
complexes and cyclopentadienyl complexes; coordinative unsaturation, oxidative addition
reactions, insertion reactions, fluxional molecules and their characterization; Compounds with
metal-metal bonds and metal atom clusters.

14. Main Group Chemistry: Boranes, borazines, phosphazenes and cyclic phosphazene, silicates
and silicones, Interhalogen compounds; Sulphur - nitrogen compounds, noble gas compounds.

15. General Chemistry of 'f' Block Elements: Lanthanides and actinides; separation, oxidation
states, magnetic and spectral properties; lanthanide contraction.

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Paper-II

1. Delocalised Covalent Bonding: Aromaticity, anti-aromaticity; annulenes, azulenes,

tropolones, fulvenes, sydnones.

2. (i) Reaction Mechanisms: General methods (both kinetic and non-kinetic) of study of
mechanism of organic reactions: isotopic method, cross-over experiment, intermediate
trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of
reactions.

(ii) Reactive Intermediates: Generation, geometry, stability and reactions of carbonium ions
and carbanions, free radicals, carbenes, benzynes and nitrenes.

(iii) Substitution Reactions: SN1, SN2 and SNi mechanisms; neighbouring group participation;
electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic
compounds-pyrrole, furan, thiophene and indole.

(iv) Elimination Reactions: E1, E2 and E1cb mechanisms; orientation in E2 reactions-Saytzeff

and Hoffmann; pyrolytic syn elimination - Chugaev and Cope eliminations.

(v) Addition Reactions: Electrophilic addition to C=C and C=C; nucleophilic addition to C=0, C=N,
conjugated olefins and carbonyls.

(vi) Reactions and Rearrangements:

(a) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer-Villiger, Favorskii, Fries, Claisen, Cope,

Stevens and WagnerMeerwein rearrangements.

(b) Aldol condensation, Claisen condensation, Dieckmann, Perkin, Knoevenagel, Witting,

Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloin
condensations; Fischer indole synthesis, Skraup synthesis, Bischler-Napieralski, Sandmeyer,
Reimer-Tiemann and Reformatsky reactions.

3. Pericyclic Reactions: Classification and examples; Woodward Hoffmann rules - electro cyclic
reactions, cycloaddition reactions [2+2 and 4+2] and sigma tropic shifts [1, 3; 3, 3 and 1, 5] FMO
approach.

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4. (i) Preparation and Properties of Polymers: Organic polymers-polyethylene, polystyrene,
polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.

(ii) Biopolymers: Structure of proteins, DNA and RNA.

5. Synthetic Uses of Reagents: OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3,
LiAlH4, NaBH4, n-BuLi and MCPBA.

6. Photochemistry: Photochemical reactions of simple organic compounds, excited and ground

states, singlet and triplet states, Norrish-Type I and Type II reactions.

7. Spectroscopy: Principle and applications in structure elucidation: (i) Rotational: Diatomic

molecules; isotopic substitution and rotational constants.

(ii) Vibrational: Diatomic molecules, linear triatomic molecules, specific frequencies of

functional groups in polyatomic molecules.

(iii) Electronic: Singlet and triplet states; N→π* and ππ*→ transitions; application to
conjugated double bonds and conjugated carbonyls-Woodward-Fieser rules; Charge transfer
spectra.

(iv) Nuclear Magnetic Resonance (1H NMR): Basic principle; chemical shift and spin-spin
interaction and coupling constants.

(v) Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.